The electronic structure of trifluorophosphine studied by photoelectron spectroscopy with variable photon energy

Abstract

The photoelectron spectrum of PF₃ has been measured using synchrotron radiation. Relative partial photoionization cross-section and branching ratio data are reported for the valence bands (8–24 eV) over the photon-energy range 30–95 eV. Molecular orbitals regarded previously as purely fluorine Ione pair in composition are shown to have significant phosphorus 3p character. Comparison of the results obtained on PF₃ with those obtained previously on [Ni(PF₃)₄] shows that the complex molecular orbitals of the latter derived from the 5e orbitals of PF₃ have some nickel 3d character. Metal-to-phosphorus back donation, proposed to occur through the 7e PF₃ molecular orbitals, is thus shown also to involve the 5e.